EP0906372A1 - Preparations de leuco-colorant a cuve sous forme granulaire - Google Patents

Preparations de leuco-colorant a cuve sous forme granulaire

Info

Publication number
EP0906372A1
EP0906372A1 EP97927136A EP97927136A EP0906372A1 EP 0906372 A1 EP0906372 A1 EP 0906372A1 EP 97927136 A EP97927136 A EP 97927136A EP 97927136 A EP97927136 A EP 97927136A EP 0906372 A1 EP0906372 A1 EP 0906372A1
Authority
EP
European Patent Office
Prior art keywords
dye
leucocupine
weight
preparations
reducing agent
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
EP97927136A
Other languages
German (de)
English (en)
Other versions
EP0906372B1 (fr
Inventor
Manfred GÄNG
Rudolf KRÜGER
Peter Miederer
Eberhard Beckmann
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Dystar Textilfarben GmbH and Co Deutschland KG
Original Assignee
BASF SE
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by BASF SE filed Critical BASF SE
Publication of EP0906372A1 publication Critical patent/EP0906372A1/fr
Application granted granted Critical
Publication of EP0906372B1 publication Critical patent/EP0906372B1/fr
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B67/00—Influencing the physical, e.g. the dyeing or printing properties of dyestuffs without chemical reactions, e.g. by treating with solvents grinding or grinding assistants, coating of pigments or dyes; Process features in the making of dyestuff preparations; Dyestuff preparations of a special physical nature, e.g. tablets, films
    • C09B67/0071—Process features in the making of dyestuff preparations; Dehydrating agents; Dispersing agents; Dustfree compositions
    • C09B67/0077—Preparations with possibly reduced vat, sulfur or indigo dyes
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
    • D06P1/00—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed
    • D06P1/22—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using vat dyestuffs including indigo
    • D06P1/221—Reducing systems; Reducing catalysts
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
    • D06P3/00—Special processes of dyeing or printing textiles, or dyeing leather, furs, or solid macromolecular substances in any form, classified according to the material treated
    • D06P3/58—Material containing hydroxyl groups
    • D06P3/60—Natural or regenerated cellulose
    • D06P3/6025—Natural or regenerated cellulose using vat or sulfur dyes

Definitions

  • the present invention relates to new leucocupine dye preparations in granular form, containing as essential constituents leucocupine dye, alkali metal hydroxide and a mixture of 10 to 100% by weight of an ⁇ -hydroxy-C 4 -C 4 -alkylsulfinic acid, one of its salts or derivatives and 0 up to 90% by weight of hydro sulfite as reducing agent.
  • the invention further relates to the production of these leucocupine dye preparations and their use for dyeing cellulosic textile material.
  • Indigo dyes especially indigo itself and its bromine derivatives such as brilliant indigo
  • anthraquinone dyes especially nitroviolanthrone (C.I. Vat Green 9)
  • vat dyes for a long time, which are used for dyeing cellulose-containing textile material.
  • the water-insoluble vat dye For dyeing, the water-insoluble vat dye must first be converted (reduction) to the water-soluble fiber-affine leuco form, which is then oxidized again to the water-insoluble vat dye pigment after being drawn onto the material to be colored.
  • the vat dye is chopped in an alkaline medium in front of the dye bath by the addition of inorganic reducing agents such as hydrosulfite (sodium dithionite) and thiourea dioxide or else organic reducing agents such as hydroxyacetone. Additional machine-dependent proportions of reducing agents are consumed during the dyeing, since part of the leuco dye is oxidized by air contact in the air passages and on the dye bath surface and has to be re-choked, which is why reducing agents must also be added to the dye bath.
  • inorganic reducing agents such as hydrosulfite (sodium dithionite) and thiourea dioxide or else organic reducing agents such as hydroxyacetone.
  • a disadvantage of combining the vat dye with the reducing agents mentioned is the high pollution of the dyeing wastewater by sulfate (about 3500 to 5000 mg / l, measured in the wastewater of an indigo dyeing plant) in the case of hydrosulfite or by oxygen-consuming substances (COD values of approx. 8000 mg oxygen / l, measured in the waste water of an indigo dyeing plant) in the case of hydroxyacetone.
  • indigo powdery solid to pasty preparations of leuco form are also described, which contain as stabilizers polyhydroxy compounds, such as glycerol and in particular compounds derived from sugars, for example molasses, in a mixture with alkali or zinc dust (DE-PS 200 914 and .
  • GB-PS-276 023 also discloses the production of powdered leuco dye preparations by heating a mixture of unreduced vat dye, glycol, alkali, hydrosulfite and sodium sulfate and drying in an open kettle and subsequent grinding.
  • the sulfate content of the dyeing wastewater can be effectively reduced, but these preparations are generally difficult to dose, since the dry preparations also tend to clump and they dissolve only slowly in the dye bath. In the latter case, the sulfate load is even increased, since sulfate is also added to the preparations, which already contain the sulfate resulting from the reduction of the dye in the mixture described above.
  • a dyeing process is known from WO-A-94/23114 in which indigo is used in a pre-reduced form as an aqueous, alkaline solution obtained in the catalytic hydrogenation.
  • indigo is used in a pre-reduced form as an aqueous, alkaline solution obtained in the catalytic hydrogenation.
  • the wastewater pollution caused by organic substances is eliminated, and the sulfate pollution is reduced to the amount of hydrosulfite required by air contact during the dyeing process.
  • the leuco indigo solution used is sensitive to oxidation and must be handled and stored in the absence of oxygen.
  • the high water ballast of this solution is a hindrance both during storage and during transport.
  • WO-A-95/05421 describes leucoindigo preparations in granular form which contain leukoindigo and alkali metal hydroxide as essential components. These granules, too, do not always have satisfactory oxidation stability when stored in air for a prolonged period, especially in high air humidity.
  • leucoindigo granules stabilized by hydrosulfite addition are described in DE-A-1 9502 968, which has not been previously published.
  • the object of the invention was to provide leucocupine dye preparations which do not have the disadvantages mentioned, are stable to oxidation and can advantageously be used for dyeing. 5
  • leucocupine dye preparations have been found in granular form which, as essential constituents, leucocupine dye, alkali metal hydroxide and a mixture of 10 to 100% by weight of an ⁇ -hydroxy-C 4 -alkyl sulfinic acid, one of its 10 salts or derivatives and 0 to Contain 90% by weight of hydrosulfite as reducing agent.
  • the preparations according to the invention generally contain 20 to 25 80% by weight, preferably 50 to 70% by weight, leucocupine dye, 5 to 55% by weight, preferably 5 to 20% by weight, reducing agent and 3 to 20% by weight .-%, preferably 4 to 10 wt .-%, alkali metal hydroxide.
  • leuco forms of anthraquinones and the leuco forms of indigoid vat dyes can be used as leucocupine dyes.
  • vat dyes are C.I. Vat 35 Green 9 and especially indigo and tetrabromo indigo (brilliant indigo).
  • the preparations according to the invention contain ⁇ -hydroxy-C 1 -C 4 -alkylsulfinic acids (hereinafter briefly sulfin
  • sodium salt can be used.
  • preferred examples are ⁇ -hydroxyethylsulfinic acid, ⁇ -hydroxypropylsulfinic acid and ⁇ -hydroxylbutylsulfinic acid and their sodium salts and in particular hydroxymethylsulfinic acid and hydroxymethylsulfinic acid sodium salt.
  • the leucocupa dye preparations according to the invention containing sulfinic acids are distinguished by particular stability. They are so stable during production and storage that they can withstand long drying times and can be stored in humid, hot air (suitable for use in the tropics).
  • preparations according to the invention additionally contain hydro-sulfite as reducing agent, then they are also particularly readily and rapidly soluble (spontaneously soluble). Any parts reoxidized during handling or dyeing are immediately reduced again.
  • mixtures of the sulfinic acids with hydrosulfite are used, their composition is preferably 85 to 15, particularly preferably 80 to 20 and very particularly preferably 60 to 40% by weight of sulfinic acid and preferably 15 to 85, particularly preferably 20 to 80 and very particularly preferably 40 to 60 wt .-% hydrosulfite.
  • Potassium hydroxide and especially sodium hydroxide are particularly suitable as alkali metal hydroxide. Mixtures of alkali metal hydroxides can of course also be used.
  • leucocupine dye is converted into the readily soluble alkali metal salts by the hydroxide.
  • leuco indigo forms the mono- and / or the di-salt, for example.
  • the molar ratio of leucocupine dye and alkali metal hydroxide is therefore advantageously about 1: 1 to 1:10, preferably 1: 1, up to the molar ratio required to convert all the free hydroxyl groups contained into the salt form.
  • amounts of reducing agent which are well below 50% by weight, in particular at a maximum of 25% by weight, based on the leuco vat dye, are sufficient to stabilize the leucocupa dye when the granule preparation is stored (protection against reoxidation).
  • an amount of reducing agent is selected in the upper range of the weight content mentioned above for the preparations according to the invention (about 40 to 55% by weight), ie based on to the leucocupine dye, up to about 65% by weight and if sulfinic acid and hydrosulfite are used as the common reducing agent, in which the hydrosulfite content is at least 50% by weight, the reoxidized portion of the vat dye which is inevitably formed by air contact during the dyeing process can be used be compared directly, no further reducing agent then has to be added to the dyebath.
  • This proportion of reducing agent can be adapted to the dyeing system used in each case by slight variation.
  • the amount of the preferred reducing agent mixture of hydroxymethylsulfinic acid sodium salt and hydrosulfite required for stabilization is generally 5 to 30% by weight, in particular 10 to 20% by weight, based on leukoindigo a preparation with a preferred composition of 55 to 75% by weight of leuco indigo, 10 to 20% by weight of the reducing agent mixture and 10 to 20% by weight of alkali metal hydroxide.
  • Essential for the stabilization of the leucocupa dye against reoxidation is its permanent, uniform mixing with the reducing agent, which is due to the granulate shape according to the invention (generally spherical particles with an average particle size of generally 0.1 to 2 mm, preferably 0.5, are predominantly located up to 1.5 mm, before) is guaranteed.
  • the proportion of hydrosulfite which only serves to compensate for the reoxidation during dyeing, and also the granules which have already been sufficiently stabilized by the reducing agent mixture or the sulfinic acid alone, can subsequently be given as a solid to mix.
  • These mixtures can be particularly easily adapted to the requirements of the respective dyeing system.
  • the catalytic hydrogenation itself can be carried out, for example, by reducing an alkaline indigo dough (usually 10 to 35% by weight indigo, 2 to 10% by weight alkali metal hydroxide) using Raney nickel as a catalyst at a hydrogen pressure of im generally 2 to 10 bar and a temperature of usually 60 to 90 ° C.
  • an alkaline indigo dough usually 10 to 35% by weight indigo, 2 to 10% by weight alkali metal hydroxide
  • Raney nickel as a catalyst at a hydrogen pressure of im generally 2 to 10 bar and a temperature of usually 60 to 90 ° C.
  • the leucoindigo solutions obtained generally contain 10 to 35, preferably 15 to 30 and particularly preferably 20 to 25% by weight of leukoindigo.
  • the alkali leucocupine dye solutions are evaporated to dryness together with a solution or suspension of the chosen reducing agent in water and / or an organic solvent with the exclusion of oxygen, advantageously after inerting with a protective gas such as nitrogen, and with thorough mixing.
  • the leucocupine dye solution and the reducing agent solution (or suspension) are preferably mixed before or during the drying process, but the reducing agent can also be added directly to the leucocupine dye solution as a solid.
  • Suitable organic solvents for the preparation of the reducing agent solution or suspension are, in particular, water-miscible solvents.
  • Preferred examples are C 1 -C 4 alcohols, especially methanol, and glycols, especially ethylene glycol, and glycol ethers, which of course can also be used in the form of mixtures.
  • Another interesting process variant consists in producing the sulfinic acid or its salt in situ during the drying of the leuco-indigo solution.
  • the preparation present after drying contains sulfinic acid and hydrosulfite as reducing agents.
  • the product temperature required for drying depends on whether or not the process is carried out under reduced pressure and is usually 50 to 90 ° C. or 105 to 130 ° C.
  • Apparatus suitable for industrial scale are therefore e.g. Tumble dryers, paddle dryers and positively cleaned contact dryers, in which drying is preferably carried out under reduced pressure (about 10 to 500 mbar).
  • reduced pressure about 10 to 500 mbar
  • the process according to the invention can advantageously also be carried out in a spray drying installation, such as a spray tower and in particular a spray fluidized bed, in which the water is evaporated while being gassed with hot inert gas, preferably nitrogen.
  • a spray drying installation such as a spray tower and in particular a spray fluidized bed, in which the water is evaporated while being gassed with hot inert gas, preferably nitrogen.
  • the dried product can be obtained here directly in the desired particle size.
  • the new leucocupine dye preparations in granular form can be produced continuously in a simple manner.
  • the dried products only contain a small amount (approximately ⁇ 4% by weight) of unreduced vat dye.
  • the leucocupine dye preparations according to the invention are advantageously suitable for dyeing cellulosic textile material.
  • the dyeings obtained correspond completely to the requirements.
  • the pollution of waste water with sulfur-containing inorganic compounds is drastically reduced compared to the use of non-reduced dyes.
  • the dyeing can also be carried out without further addition of reducing agent to the dye bath.
  • the granules obtained had an average particle diameter of 2 mm.
  • a water-insoluble fraction (by-products and reoxidized indigo) of ⁇ 1% by weight was determined by extraction with water in Soxleth.
  • the granules contained approximately 72.4% by weight of leucoindigo, 4.3% by weight of hydroxymethylsulfinic acid sodium salt, 4.3% by weight of hydrosulfite and 13.8% by weight of sodium hydroxide.
  • the granules obtained had an average particle diameter of 1.5 mm.
  • a water-insoluble fraction of ⁇ 4 wt .-% determined.
  • the granules contained approximately 64% by weight of leuco indigo, 7% by weight of hydroxymethylsulfinic acid sodium salt, 7% by weight of sodium sulfite and 20% by weight of sodium hydroxide.
  • the granules obtained had an average particle diameter of 1.5 mm.
  • a water-insoluble fraction of about 4% by weight was determined by extraction with water in Soxleth.
  • the granules contained approximately 73% by weight of leuco indigo, 11% by weight of nitrilotrimethanesulfinic acid and 15% by weight of sodium hydroxide.
  • Example 1 A solution of 22% by weight leukoindigo (calculated as free acid), 5% by weight sodium hydroxide, 3.3% by weight hydroxymethylsulfinic acid sodium salt (99%) and 69.7% by weight water was analogous Example 1 dried.
  • the granules After coarse comminution, the granules had an average particle diameter of 1.5 mm. A water-insoluble fraction of ⁇ 1% by weight was determined by extraction with water in Soxleth. The granules contained approx. 71% by weight
  • Leucoindigo 10.5% by weight hydroxymethylsulfinic acid sodium salt and 16.5% by weight sodium hydroxide.
  • the dyed yarn showed the same nuance, depth of color and fastness as one in a conventional manner with the constant addition of

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Organic Chemistry (AREA)
  • Coloring (AREA)
  • Medicinal Preparation (AREA)
  • Cosmetics (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)
  • Paper (AREA)
  • Chemical Or Physical Treatment Of Fibers (AREA)
  • Detergent Compositions (AREA)
  • Medicines Containing Plant Substances (AREA)

Abstract

L'invention concerne des préparations de leuco-colorant à cuve sous forme granulaire, contenant comme principaux constituants un leuco-colorant à cuve, de l'hydroxyde de métal alcalin et un mélange de 10 à 100 % en poids d'un acide α-hydroxy-alkylsulfinique C1-C4, d'un de leurs sels ou dérivés et entre 0 et 90 % en poids d'hydrosulfite comme agent réducteur. L'invention concerne en outre la production de ces préparations et leur utilisation pour teinter des matériaux textiles contenant de la cellulose.
EP97927136A 1996-06-18 1997-06-05 Preparations de leuco-colorant a cuve sous forme granulaire Expired - Lifetime EP0906372B1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE19624208 1996-06-18
DE19624208A DE19624208A1 (de) 1996-06-18 1996-06-18 Leukoküpenfarbstoff-Präparationen in Granulatform
PCT/EP1997/002912 WO1997048770A1 (fr) 1996-06-18 1997-06-05 Preparations de leuco-colorant a cuve sous forme granulaire

Publications (2)

Publication Number Publication Date
EP0906372A1 true EP0906372A1 (fr) 1999-04-07
EP0906372B1 EP0906372B1 (fr) 2001-10-17

Family

ID=7797219

Family Applications (1)

Application Number Title Priority Date Filing Date
EP97927136A Expired - Lifetime EP0906372B1 (fr) 1996-06-18 1997-06-05 Preparations de leuco-colorant a cuve sous forme granulaire

Country Status (15)

Country Link
US (1) US6007587A (fr)
EP (1) EP0906372B1 (fr)
JP (1) JP2000512673A (fr)
CN (1) CN1084770C (fr)
AT (1) ATE207102T1 (fr)
AU (1) AU3172797A (fr)
BR (1) BR9709806A (fr)
DE (2) DE19624208A1 (fr)
EA (1) EA001854B1 (fr)
ES (1) ES2166089T3 (fr)
ID (1) ID17165A (fr)
TR (1) TR199802635T2 (fr)
TW (1) TW455619B (fr)
UA (1) UA54434C2 (fr)
WO (1) WO1997048770A1 (fr)

Families Citing this family (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6780205B2 (en) * 2001-08-21 2004-08-24 E. I. Du Pont De Nemours And Company Vat acid dyeing of textile fibers
US6942706B2 (en) * 2002-08-20 2005-09-13 Invista North America S.A.R.L. Vat acid dyeing of textile fibers
CN101349016B (zh) * 2007-07-20 2010-05-26 上海市毛麻纺织科学技术研究所 染料复合还原剂及采用该复合还原剂染色的方法
CN102153885A (zh) * 2011-03-17 2011-08-17 浙江长征化工有限公司 一种液体靛蓝染料的制备方法及产品
CN103304267B (zh) * 2012-03-12 2014-12-17 崔骥 水泥结构着色剂及着色方法
CN105602287B (zh) * 2016-01-22 2018-01-05 天津工业大学 一种新型预混还原剂的复合靛蓝染料的制备方法
TN2020000011A1 (en) * 2017-08-11 2021-10-04 Archroma Ip Gmbh Methods of making leucoindigo salt solutions with very low aniline content

Family Cites Families (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE200914C (fr) *
DE235047C (fr) * 1908-10-14
GB190924605A (en) * 1909-10-26 1910-08-25 Columbia Postal Supply Co Improvements in Mail Marking Machines.
FR417071A (fr) * 1909-11-10 1910-11-05 Basf Ag Préparations solides et stables à base d'indigo blanc
GB276023A (en) * 1926-08-16 1928-11-15 Geigy Ag J R Manufacture of preparations of leuco-compounds of vatdyestuffs
DE1071653B (de) * 1958-06-04 1959-12-24 Badische Anilin- S. Soda-Fabrik Aktiengesellschaft, Ludwigshafen/Rhein Verfahren zum Färben von Textilgarnen mit Küpen- und/oder Schwefelfarbstoffen auf Garnoder Spritzfärbemaschinen
GB916519A (en) * 1960-01-20 1963-01-23 Holliday Co Ltd L B Improvements in or relating to sulphurised vat dyestuffs in solubilised form
GB884027A (en) * 1960-01-20 1961-12-06 Holliday Co Ltd L B Improvements in or relating to sulphurised vat dyestuffs in solubilised form
US4113427A (en) * 1976-04-26 1978-09-12 Royce Chemical Company Process for dyeing cellulosic textiles with vat and sulfur dyes
TW251325B (fr) * 1993-03-30 1995-07-11 Basf Ag
DE4327221A1 (de) * 1993-08-13 1995-02-16 Basf Ag Leukoindigo-Präparation in Granulatform
DE19502968A1 (de) * 1995-01-31 1996-08-01 Basf Ag Leukoküpenfarbstoff-Präparationen in Granulatform

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO9748770A1 *

Also Published As

Publication number Publication date
CN1084770C (zh) 2002-05-15
TR199802635T2 (xx) 1999-03-22
DE19624208A1 (de) 1998-01-02
EA199900013A1 (ru) 1999-06-24
CN1222175A (zh) 1999-07-07
AU3172797A (en) 1998-01-07
BR9709806A (pt) 1999-08-10
ATE207102T1 (de) 2001-11-15
JP2000512673A (ja) 2000-09-26
WO1997048770A1 (fr) 1997-12-24
TW455619B (en) 2001-09-21
EA001854B1 (ru) 2001-08-27
ID17165A (id) 1997-12-04
UA54434C2 (uk) 2003-03-17
EP0906372B1 (fr) 2001-10-17
ES2166089T3 (es) 2002-04-01
DE59704980D1 (de) 2001-11-22
US6007587A (en) 1999-12-28

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